Fibre-reactive chromium complex dyes, process for their manufacture and use thereof to dye cellulose or wool

ABSTRACT

Novel chromium complex dyes are disclosed which have the formula ##STR1## wherein S 1  represents a hydrogen or halogen atom, a nitro group, a sulpho group, an alkyl or alkoxy radical, an acylamino or arylazo group, 
     S 2  represents a hydrogen or halogen atom, a nitro group, a sulpho group, an alkyl or alkoxy radical, 
     S 3  represents a hydrogen atom, a nitro group or a halogen atom, 
     P is 1 or 2, 
     R represents a fluorochloropyrimidyl or fluorotriazinyl radical, a chloroacetyl, bromoacetyl, α-chloro- or α-bromoacryloyl radical or an α,β-dichloro- or α,β-dibromopropionyl radical, and 
     K.sup.⊕  represents a cation.

This is a divisional of application Ser. No. 199,789 filed on Oct. 23,1980, now U.S. Pat. No. 4,432,898 which in turn is a continuation ofapplication Ser. No. 971,140, filed on Dec. 19, 1978, now abandoned,which in turn is a continuation of application Ser. No. 805,754, filedJune 13, 1977, now abandoned.

The invention relates to chromium complex dyes of the formula ##STR2##wherein S₁ represents a hydrogen or halogen atom, a nitro group, asulpho group, an alkyl or alkoxy radical, an acylamino or arylazo group,

S₂ represents a hydrogen or halogen atom, a nitro group, a sulpho group,an alkyl or alkoxy radical,

S₃ represents a hydrogen atom, a nitro group or a halogen atom,

p is 1 or 2,

R represents a fluorochloropyrimidyl or fluorotriazinyl radical, achloroacetyl, bromoacetyl, α-chloro- or α-bromoacryloyl radical or anα,β-dichloro- or α,β-dibromopropionyl radical, and

K.sup.⊕ represents a cation.

The term "halogen" is to be understood as meaning herein fluorine,bromine and, preferably, chlorine atoms, and the terms "alkyl" and"alkoxy" comprise in particular low molecular radicals, i.e. alkyl andalkoxy radicals each having 1 to 4 carbon atoms. The term "acylamino"denotes herein in particular alkanoylamino and alkoxycarbonylaminogroups, wherein the hydrocarbon radical contains 1 to 4 carbon atoms,for example acetylamino or ethoxycarbonylamino groups. Possible arylazogroups are naphthyl and preferably phenylazo groups which can besubstituted for example by sulpho, chlorine, bromine, methyl, methoxy ornitro.

The dyes of the present invention are obtained by reacting one of theazo dyes of the formulae ##STR3## with a chromium donor to give the 1:1chromium complex and reacting this latter with the other azo dye of theabove formulae to give the 1:2 chromium complex and, before or after thechroming, reacting the NH₂ groups of the compounds of the formulae (2)and (3) with an acylating agent which affords the radical R.

It is preferable to prepare firstly the 1:2 chromium complex of the azodyes of the formulae (2) and (3), and then to react this compound withan acylating agent which affords the radical R.

In particular, the starting material is a chromium complex of theformula ##STR4## wherein S₁ ' represents a nitro group, a chlorine atom,a sulpho or sulphophenylazo group, an alkyl or alkoxy radical, analkanoylamino or alkoxycarbonylamino group,

S₂ ' represents a hydrogen or chlorine atom, a nitro group, a sulphogroup, or a lower molecular alkyl or alkoxy radical,

S₃ ' represents a hydrogen atom or a nitro group, and

K.sup.⊕ represents a cation,

or is a chromium complex of the formula ##STR5## wherein K.sup.⊕ is asdefined above, one of the symbols X₁, X₂ and X₃ represents, or any tworepresent, hydrogen, and the other two represent, or the thirdrepresents, chlorine, nitro, methyl, methoxy, or sulpho.

These chromium complexes are obtained by methods which are known per se.For example, the 1:1 chromium complex of the compound of the formula (3)is prepared by reacting the metal-free compound in acid medium with asalt of trivalent chromium such as chromium chloride, chromium fluorideor chromium sulphate. The 1:1 complex is subsequently reacted in neutralto weakly alkaline medium with a compound of the formula (2).

Examples of suitable diazo components for the azo compounds of theformula (2) are: anthranilic acid, 2-amino-1-hydroxybenzene, 4- or5-chloro-2-amino-1-hydroxybenzene, 4- or5-nitro-2-amino-1-hydroxybenzene, 4-methyl-2-amino-1-hydroxybenzene,4-methoxy-2-amino-1-hydroxybenzene,4,6-dichloro-2-amino-1-hydroxybenzene,4,6-dinitro-2-amino-1-hydroxybenzene,4-chloro-5-nitro-2-amino-1-hydroxybenzene,4-chloro-6-nitro-2-amino-1-hydroxybenzene,6-chloro-4-nitro-2-amino-1-hydroxybenzene,6-nitro-4-methyl-2-amino-1-hydroxybenzene, 4-(m- orp-sulphophenylazo)-2-amino-1-hydroxybenzene,4-nitro-2-aminophenol-6-sulphonic acid or6-nitro-2-aminophenol-4-sulphonic acid.

The diazo components with nitro groups are preferred, especially 4- or5-nitrophenol, and the mixtures thereof.

As coupling components aminonaphtholsulphonic acids are used, such as1-amino-5-naphthol-7-sulphonic acid, 1-amino-8-naphthol-4-sulphonicacid, or 2-amino-6-naphthol-8-sulphonic acid, and preferably2-amino-8-naphthol-6-sulphonic acid and 2-amino-5-naphthol-7-sulphonicacid.

Suitable acylating agents which afford the radical R are chloroacetylchloride, bromoacetyl chloride, α,β-dichloro- or α,β-dibromopropionylchloride, α-chloro- or α-bromoacrylyl chloride,5-chloro-2,4,6-trifluoropyrimidine, 2,4,6-trifluorotriazine andfluorotriazine compounds of the formula ##STR6## wherein Z represents aremovable radical, in particular a fluorine atom, and R₁ represents asubstituted or unsubstituted amino group or a free or etherified oxy orthio group, for example the NH₂ group, an amino group which is mono- ordisubstituted by C₁ -C₄ -alkyl radicals; a C₁ -C₄ -alkoxy radical, a C₁-C₄ -alkylmercapto group, an arylamino group, in paticular phenylaminogroup, or a phenylamino, phenoxy, mono- or disulphophenoxy group etc.which is substituted by methyl, methoxy, chlorine and, in particular, bysulpho.

Examples of such triazine compounds are: 2,4-difluoro-6-aminotriazine,2,4-difluoro-6-methylaminotriazine, 2,4-difluoro-6-ethylaminotriazine,2,4-difluoro-6-phenylaminotriazine, 2,4-difluoro-6-(2'-, 3'- or4'-sulphophenyl)-aminotriazine, 2,4-difluoro-6-(2',4'- or 3',4'- or2',5'- or 4',5'-disulphophenyl)-aminotriazine,2,4-difluoro-6-dimethylaminotriazine, 2,4-difluoro-6-methoxytriazine,2,4-difluoro-6-(β-methoxyethoxy)-triazine,2,4-difluoro-6-methylmercaptotriazine,2,4-difluoro-6-phenylmercapto-triazine.

The acylation is effected by methods which are known per se, for exampleby addition of the acylating agent to an aqueous solution of the 1:2chromium complex in weakly acid to weakly alkaline medium, for examplein the presence of sodium hydrogen carbonate.

Preferred acyl radicals are the α-bromoacryloyl and α,β-dibromopropionylradical. The former can be introduced either with bromacrylyl chlorideor be obtained from the α,β-dibromopropionyl radical by removal ofhydrogen bromide. The same also applies in respect of theα-chloroacrylyl radical. The 4,6-difluorotriazinyl-(2) or4-fluoro-6-alkyl- or -arylaminotriazinyl-(2) radicals are also ofinterest.

The novel dyes are suitable for dyeing and printing cellulose or naturalprotein material, in particular cotton and shrinkproofed (chlorinated)wool. They can also be used in the exhaustion process and in the paddingand transfer printing process. In the two first named processes, thedyes are advantageously applied to the textile fabric from aqueousweakly acid liquors which contain a levelling agent. The transferprinting is effected by transferring the dye by a heat treatment, in thepresence of moisture, from a carrier to the textile fabric.

The dyeings and prints obtained are characterised by good fastnessproperties, such as lightfastness, fastness to rubbing and, above all,by good wetfastness properties, such as fastness to washing, fulling,perspiration, hot water and and moist heat. A particular advantage ofthe dyes of the present invention resides in the fact that they exhaustreadily and build up to deep uniform dyeings--a property which is ofgreat importance in effecting black dyeings.

In the following Examples, the parts and percentages are by weight.

EXAMPLE 1

53.4 Parts of the 1:1 chromium complex of the monoazo dye obtained inknown manner for diazotised 6-nitro-1-amino-2-naphthol-4-sulphonic acidand 2-amino-5-naphthol-7-sulphonic acid are stirred with 44.9 parts ofthe monoazo dye from diazotised 4,6-dinitro-2-aminophenol and2-amino-8-naphthol-6-sulphonic acid in 600 parts of hot water untilhomogeneity is obtained. The suspension is heated to a temperature of90° to 95° C. and adjusted to a constant pH value of 8 to 8.5 byaddition of a 2N sodium hydroxide solution, then stirred at thistemperature until it is no longer possible to detect either of the twomonoazo dyes in the resultant clear solution.

The deep black solution of the mixed complex is thereafter cooled to atemperature of 10° to 12° C. and 40 parts of sodium hydrogen carbonateare added. Then 29.5 parts of α,β-dibromopropionyl chloride are addeddropwise, with stirring, in the course of an hour. The acylatingsolution is stirred, with attendant rise to room temperature, until nomore free amino groups can be detected.

The novel dye of the following constitution ##STR7## is isolated byevaporating the solution to dryness in vacuo at 60°-70° C. It is readilysoluble in water and produces wet- and lightfast full black dyeings onshrinkproofed wool by the methods described subsequently in the dyeingprocedures.

EXAMPLE 2

53.4 Parts of the 1:1 chromium complex of the monoazo dye fromdiazotised 6-nitro-1-amino-2-naphthol-4-sulphonic acid and2-amino-5-naphthol-7-sulphonic acid are reacted with 39.35 parts of themonoazo dye from diazotised 4-chloro-2-aminophenol and2-amino-8-naphthol-6-sulphonic acid in accordance with the particularsof Example 1 to give the corresponding homogeneous mixed complex, whichis then acylated with 29.5 parts of α,β-dibromopropionyl chloride togive a reactive dye of analogous constitution. Wet- and lightfast fullblue-black shades are produced with this dye on shrinkproofed wool bythe methods described in the subsequent dyeing procedures.

EXAMPLE 3

53.4 Parts of the 1:1 chromium complex of the monoazo dye fromdiazotised 6-nitro-1-amino-2-naphthol-4-sulphonic acid and2-amino-5-naphthol-7-sulphonic acid and 40.4 parts of the monoazo dyefrom diazotised 4-nitro-2-aminophenol and 2-amino-8-naphthol-6-sulphonicacid are suspended in 600 parts of water. The suspension is adjusted toa pH value of 8 to 9 by addition of a 2N sodium hydroxide solution andreacted to the homogeneous mixed complex by stirring for 1 hour at90°-95° C. The acylation with α,β-dibromopropionyl chloride according tothe particulars of Example 1 gives a reactive dye which dyesshrinkproofed wool in full black shades of very good wet- andlightfastness.

EXAMPLE 4

53.4 Parts of the 1:1 chromium complex of the monoazo dye described inExample 1 are reacted with 40.4 parts of the monoazo dye from diazotised4-nitro-2-aminophenol and 1-amino-5-naphthol-7-sulphonic acid to givethe homogeneous mixed complex, which is then acylated withα,β-dibromopropionyl chloride as described in Example 1. The acylatingsolution is cooled with the addition of ice to 3°-5° C., adjusted to aconstant pH of 12 by addition of 5N sodium hydroxide solution andstirred for 1 hour. The clear solution is then neutralised with dilutehydrochloric acid and evaporated to dryness in vacuo at 60° to 70° C. toisolate the dye.

The novel dye of the constitution ##STR8## produces wet- and lightfastfull violet-black dyeings on shrinkproofed wool by the methods describedin the subsequent dyeing procedures.

EXAMPLE 5

53.4 Parts of the 1:1 chromium complex of the monoazo dye described inExample 1 are reacted with 46.1 parts of the monoazo dye from diazotised4-nitro-6-acetylamino-2-aminophenol and 2-amino-6-naphthol-8-sulphonicacid to give the homogeneous mixed complex, which is acylated withα,β-dibromopropionyl chloride as in Example 1. The dye obtained afterevaporation of the reaction solution dyes shrinkproofed wool in fullblack shades of very good wet- and lightfastness by the methodsdescribed in the subsequent dyeing procedures.

EXAMPLE 6

53.4 Parts of the 1:1 chromium complex of the monoazo dye described inExample 1 are reacted with 54.3 parts of the disazo dye from diazotised4-(3'-sulphophenylazo)-2-aminophenol and 2-amino-5-naphthol-7-sulphonicacid in aqueous solution at pH 8 to 9 and 90° to 95° C. to give thehomogeneous mixed complex. After acylation with 29.5 parts ofα,β-dibromopropionyl chloride in accordance with Example 1, the noveldye of the formula ##STR9## is precipitated from the solution byaddition of potassium chloride, isolated by filtration and dried invacuo at 60° to 70° C. Wet- and lightfast deep black dyeings areobtained on shrinkproofed woollen material.

A somewhat more greenish-black dye of the same colouristic properties isobtained by using 2-amino-8-naphthol-6-sulphonic acid as couplingcomponent in the disazo dye.

EXAMPLE 7

48.7 Parts of the 1:1 chromium complex of the monoazo dye fromdiazotised 1-amino-2-naphthol-4-sulphonic acid and2-amino-5-naphthol-7-sulphonic acid are stirred with 39.35 parts of themonoazo dye from diazotised 4-chloro-2-aminophenol and2-amino-5-naphthol-7-sulphonic acid in 800 parts of hot water untilhomogeneity is attained. The suspension is heated to a temperature of90° to 95° C. and adjusted to a pH value of 8 to 8.5 by addition of 2Nsodium hydroxide solution, then stirred at this temperature until it isno longer possible to detect either of the two monoazo dyes in theresultant solution.

The dark blue solution of the mixed complex is then cooled to atemperature of 10° to 12° C. and at this temperature 29.5 parts ofα,β-dibromopropionyl chloride are added dropwise, with stirring, in thecourse of 1 hour while keeping the pH at 6.5 to 7.5 with 2N sodiumhydroxide solution. The acylating solution is stirred with attendantrise in temperature until no more free amino groups can be detected. Thedye of the following constitution ##STR10## is precipitated by theaddition of sodium chloride, then filtered off and dried. It is readilysoluble in water and dyes chlorinated wool in wet- and lightfast navyblue shades by the methods described in the subsequent dyeingprocedures.

EXAMPLE 8

48.7 Parts of the 1:1 chromium complex of the monoazo dye of Example 7are reacted with 40.7 parts of the monoazo dye from diazotised4-nitro-2-aminophenol and 2-amino-8-naphthol-6-sulphonic acid in aqueoussolution at a pH of 8 to 9 and a temperature of 90° to 95° C. to givethe homogeneous mixed complex. After acylation with 29.5 parts ofα,β-dibromopropionyl chloride according to Example 7, the novel dye ofthe formula ##STR11## is precipitated from the solution by addition ofsodium chloride, then filtered off and dried. Wet- and lightfastbluish-grey dyeings are obtained on shrinkproofed woollen material.Further dyes of this kind are obtained by reacting 1:1 chromiumcomplexes of the monoazo dyes in column I of the table with the monoazodyes in column II and acylating the mixed complexes with the acidchlorides in column III. Column IV indicates the shades obtained onshrinkproofed wool.

    __________________________________________________________________________    No.                                                                              I                 II               III      IV                             __________________________________________________________________________    1  6-nitro-1-amino-                                                                        2-amino-5-                                                                            5-nitro-2-amino-                                                                       2-amino-8-                                                                            α,β-dibromo-                                                                black                             2-naphthol-4-                                                                           naphthol-7-                                                                           phenol   naphthol-6-                                                                           propionyl                                  sulphonic acid                                                                          sulphonic acid   sulphonic                                                                             chloride                                                              acid                                            2  6-nitro-1-amino-                                                                        2-amino-5-                                                                            5-nitro-4-chloro-                                                                      2-amino-8-                                                                            α,β-dibromo-                                                                blue-                             2-naphthol-4-                                                                           naphthol-7-                                                                           2-aminophenol                                                                          naphthol-6-                                                                           propionyl                                                                              black                             sulphonic acid                                                                          sulphonic acid   sulphonic                                                                             chloride                                                              acid                                            3  6-nitro-1-amino-                                                                        2-amino-5-                                                                            6-nitro-4-chloro-                                                                      2-amino-8-                                                                            α,β-dibromo-                                                                black                             2-naphthol-4-                                                                           naphthol-7-                                                                           2-aminophenol                                                                          naphthol-6-                                                                           propionyl                                  sulphonic acid                                                                          sulphonic acid   sulphonic                                                                             chloride                                                              acid                                            4  6-nitro-1-amino-                                                                        2-amino-5-                                                                            6-nitro-4-methyl-                                                                      2-amino-8-                                                                            α,β-dibromo-                                                                black                             2-naphthol-4-                                                                           naphthol-7-                                                                           2-aminophenol                                                                          naphthol-6-                                                                           propionyl                                  sulphonic acid                                                                          sulphonic acid   sulphonic                                                                             chloride                                                              acid                                            5  6-nitro-1-amino-                                                                        2-amino-5-                                                                            4-methyl-2-                                                                            2-amino-8-                                                                            chloroacetyl                                                                           black                             2-naphthol-4-                                                                           naphthol-7-                                                                           aminophenol                                                                            naphthol-6-                                                                           chloride                                   sulphonic acid                                                                          sulphonic acid   sulphonic                                                                     acid                                            6  6-nitro-1-amino-                                                                        2-amino-5-                                                                            4-methoxy-2-                                                                           2-amino-8-                                                                            α,β-dibromo-                                                                blue-                             2-naphthol-4-                                                                           naphthol-7-                                                                           aminophenol                                                                            naphthol-6-                                                                           propionyl                                                                              black                             sulphonic acid                                                                          sulphonic acid   sulphonic                                                                             chloride                                                              acid                                            7  6-nitro-1-amino-                                                                        2-amino-5-                                                                            4-nitro-2-amino-                                                                       2-amino-8-                                                                            α,β-dibromo-                                                                black                             2-naphthol-4-                                                                           naphthol-7-                                                                           phenol-6-sul-                                                                          naphthol-6-                                                                           propionyl                                  sulphonic acid                                                                          sulphonic acid                                                                        phonic acid                                                                            sulphonic                                                                             chloride                                                              acid                                            8  6-nitro-1-amino-                                                                        2-amino-5-                                                                            6-nitro-2-amino-                                                                       2-amino-8-                                                                            α,β-dibromo-                                                                black                             2-naphthol-4-                                                                           naphthol-7-                                                                           phenol-4-sul-                                                                          naphthol-6-                                                                           propionyl                                  sulphonic acid                                                                          sulphonic acid                                                                        phonic acid                                                                            sulphonic                                                                             chloride                                                              acid                                            9  6-nitro-1-amino-                                                                        2-amino-5-                                                                            4-chloro-2-amino-                                                                      2-amino-8-                                                                            α-bromoacrylyl-                                                                  blue-                             2-naphthol-4-                                                                           naphthol-7-                                                                           phenol-6-sul-                                                                          naphthol-6-                                                                           chloride black                             sulphonic acid                                                                          sulphonic                                                                             phonic acid                                                                            sulphonic                                                    acid             acid                                            10 6-nitro-1-amino-                                                                        2-amino-5-                                                                            4-methoxy-2-                                                                           2-amino-8-                                                                            α,β-dibromo-                                                                blue-                             2-naphthol-4-                                                                           naphthol-7-                                                                           aminophenol-5-                                                                         naphthol-6-                                                                           propionyl                                                                              black                             sulphonic acid                                                                          sulphonic                                                                             sulphonic acid                                                                         sulphonic                                                                             chloride                                             acid             acid                                            11 6-nitro-1-amino-                                                                        2-amino-5-                                                                            4-chloro-2-amino-                                                                      2-amino-5-                                                                            α,β-dibromo-                                                                violet                            2-naphthol-4-                                                                           naphthol-7-                                                                           phenol   naphthol-7-                                                                           propionyl                                                                              black                             sulphonic acid                                                                          sulphonic        sulphonic                                                                             chloride                                             acid             acid                                            12 6-nitro-1-amino                                                                         2-amino-5-                                                                            4-nitro-2-amino-                                                                       2-amino-5-                                                                            α,β-dibromo-                                                                black                             2-naphthol-4-                                                                           naphthol-7-                                                                           phenol   naphthol-7-                                                                           propionyl                                  sulphonic acid                                                                          sulphonic        sulphonic                                                                             chloride                                             acid             acid                                            13 6-nitro-1-amino-                                                                        2-amino-5-                                                                            5-nitro-2-amino-                                                                       2-amino-5-                                                                            α, β-dibromo-                                                               blue-                             2-naphthol-4-                                                                           naphthol-7-                                                                           phenol   naphthol-7-                                                                           propionyl                                                                              black                             sulphonic acid                                                                          sulphonic        sulphonic                                                                             chloride                                             acid             acid                                            14 6-nitro-1-amino-                                                                        2-amino-5-                                                                            4,6-dinitro-2-                                                                         2-amino-5-                                      60 , β-dibromo-                                                             black                                                                         2-naphthol-4-                                                                           naphthol-7-                                                                           aminophenol                                                                            naphthol-7-                                                                           propionyl                                  sulphonic acid                                                                          sulphonic        sulphonic                                                                             chloride                                             acid             acid                                            15 6-nitro-1-amino-                                                                        2-amino-5-                                                                            6-nitro-4-methyl-                                                                      2-amino-5-                                                                            α, β-dibromo-                                                               black                             2-naphthol-4-                                                                           naphthol-7-                                                                           2-aminophenol                                                                          naphthol-7-                                                                           propionyl                                  sulphonic acid                                                                          sulphonic        sulphonic                                                                             chloride                                             acid             acid                                            16 6-nitro-1-amino-                                                                        2-amino-5-                                                                            4-methoxy-2-                                                                           2-amino-5-                                                                            chloroacetyl-                                                                          blue-                             2-naphthol-4-                                                                           naphthol-7-                                                                           aminophenol                                                                            naphthol-7-                                                                           chloride black                             sulphonic acid                                                                          sulphonic        sulphonic                                                    acid             acid                                            17 6-nitro-1-amino-                                                                        2-amino-5-                                                                            anthranilic                                                                            2-amino-5-                                                                            chloroacetyl                                                                           blue- l - 2-naphthol-4- nap                                                   hthol-7- acid naphthol-7- c                                                   hloride black                     sulphonic acid                                                                          sulphonic        sulphonic                                                    acid             acid                                            18 6-nitro-1-amino-                                                                        2-amino-8-                                                                            4-nitro-2-                                                                             2-amino-8-                                                                            α, β-dibromo-                                                               black                             2-naphthol-4-                                                                           naphthol-6-                                                                           aminophenol                                                                            naphthol-6-                                                                           propionyl                                  sulphonic acid                                                                          sulphonic        sulphonic                                                                             chloride                                             acid             acid                                            19 6-nitro-1-amino-                                                                        2-amino-8-                                                                            4,6-dinitro-2-                                                                         2-amino-8-                                                                            α, β-dibromo-                                                               greenish-                         2-naphthol-4-                                                                           naphthol-6-                                                                           aminophenol                                                                            naphthol-6-                                                                           propionyl                                                                              black                             sulphonic acid                                                                          sulphonic        sulphonic                                                                             chloride                                             acid             acid                                            20 6-nitro-1-amino-                                                                        2-amino-8-                                                                            6-nitro-2-amino-                                                                       2-amino-8-                                                                            α, β-dibromo-                                                               black                             2-naphthol-4-                                                                           naphthol-6-                                                                           phenol-4-                                                                              naphthol-6-                                                                           propionyl                                  sulphonic acid                                                                          sulphonic                                                                             sulphonic acid                                                                         sulphonic                                                                             chloride                                             acid             acid                                            21 6-nitro-1-amino-                                                                        2-amino-8-                                                                            4-nitro-2-amino-                                                                       2-amino-6-                                                                            α-bromo-                                                                         black                             2-naphthol-4-                                                                           naphthol-6-                                                                           phenol   naphthol-8-                                                                           acrylyl                                    sulphonic acid                                                                          sulphonic        sulphonic                                                                             chloride                                             acid             acid                                            22 6-nitro-1-amino-                                                                        2-amino-8-                                                                            4,6-dinitro-2-                                                                         2-amino-6-                                                                            α-bromo-                                                                         greenish-                         2-naphthol-4-                                                                           naphthol-6-                                                                           aminophenol                                                                            naphthol-8-                                                                           acrylyl  black                             sulphonic acid                                                                          sulphonic        sulphonic                                                                             chloride                                             acid             acid                                            23 6-nitro-1-amino-                                                                        2-amino-8-                                                                            6-nitro-2-amino-                                                                       2-amino-6-                                                                            α, β-dichloro-                                                              black                             2-naphthol-4-                                                                           naphthol-6-                                                                           phenol-4-                                                                              naphthol-8-                                                                           propionyl-                                 sulphonic acid                                                                          sulphonic                                                                             sulphonic acid                                                                         sulphonic                                                                             chloride                                             acid             acid                                            24 6-nitro-1-amino-                                                                        2-amino-5-                                                                            4,6-dinitro-2-                                                                         1-amino-5-                                                                            chloroacetyl                                                                           black                             2-naphthol-4-                                                                           naphthol-7-sul-                                                                       aminophenol                                                                            naphthol-7-sul-                                                                       chloride                                   sulphonic acid                                                                          phonic acid      phonic acid                                     25 6-nitro-1-amino-                                                                        2-amino-5-                                                                            4-chloro-2-amino-                                                                      1-amino-5-                                                                            α, β-dibromo-                                                               violet                            2-naphthol-4-                                                                           naphthol-7-                                                                           phenol   naphthol-7-                                                                           propionyl-                                                                             black                             sulphonic acid                                                                          sulphonic        sulphonic                                                                             chloride                                             acid             acid                                            26 6-nitro-1-amino-                                                                        2-amino-5-                                                                            4-nitro-2-amino-                                                                       2-amino-8-                                                                            α, β-dibromo-                                                               black                             2-naphthol-4-                                                                           naphthol-7-                                                                           phenol   naphthol-5-                                                                           propionyl-                                 sulphonic acid                                                                          sulphonic        sulphonic                                                                             chloride                                             acid             acid                                            27 6-nitro-1-amino-                                                                        2-amino-5-                                                                            6-nitro-4-methyl-                                                                      2-amino-8-                                                                            α, β-dibromo-                                                               black                             2-naphthol-4-                                                                           naphthol-7-                                                                           2-aminophenol                                                                          naphthol-5-                                                                           propionyl-                                 sulphonic acid                                                                          sulphonic        sulphonic                                                                             chloride                                             acid             acid                                            28 1-amino-2-                                                                              2-amino-5-                                                                            4-chloro-2-amino-                                                                      2-amino-5-                                                                            α, β-dibromo-                                                               navy                              naphthol-4-                                                                             naphthol-7-                                                                           phenol   naphthol-7-                                                                           propionyl-                                                                             blue                              sulphonic acid                                                                          sulphonic        sulphonic                                                                             chloride                                             acid             acid                                            29 1-amino-2-                                                                              2-amino-5-                                                                            5-nitro-2-amino-                                                                       2-amino-5-                                                                            α, β-dibromo-                                                               navy                              naphthol-4-                                                                             naphthol-7-                                                                           phenol   naphthol-7-                                                                           propionyl-                                                                             blue                              sulphonic acid                                                                          sulphonic        sulphonic                                                                             chloride                                             acid             acid                                            30 1-amino-2-                                                                              2-amino-5-                                                                            4,6-dinitro-2-                                                                         2-amino-8-                                                                            α, β-dibromo-                                                               black                             naphthol-4-                                                                             naphthol-7-                                                                           aminophenol                                                                            naphthol-6-                                                                           propionyl-                                 sulphonic acid                                                                          sulphonic        sulphonic                                                                             chloride                                             acid             acid                                            31 1-amino-2-naphthol-                                                                     2-amino-5-                                                                            5-nitro-2-amino-                                                                       2-amino-5-                                                                            α-bromoacryl                                                                     navy                              4-sulphonic acid                                                                        naphthol-7-                                                                           phenol   naphthol-7-                                                                           chloride blue                                        sulphonic        sulphonic acid                                               acid                                                             32 1-amino-2-naphthol-                                                                     2-amino-5-                                                                            5-nitro-4-chloro-                                                                      2-amino-5-                                                                            α, β-dibromo-                                                               navy                              4-sulphonic acid                                                                        naphthol-7- 2-aminophenol                                                             naphthol-7-                                                                            propionyl-                                                                            blue                                                 sulphonic        sulphonic acid                                                                        chloride                                             acid                                                             33 1-amino-2-naphthol-                                                                     2-amino-5-                                                                            4-methoxy-2-                                                                           2-amino-5-                                                                            α, β-dibromo-                                                               navy                              4-sulphonic acid                                                                        naphthol-7-                                                                           aminophenol                                                                            naphthol-7-                                                                           propionyl-                                                                             blue                                        sulphonic        sulphonic acid                                                                        chloride                                             acid                                                             34 1-amino-2-naphthol-                                                                     2-amino-5-                                                                            6-nitro-4-methyl-                                                                      2-amino-8-                                                                            α, β-dibromo-                                                               black                             4-sulphonic acid                                                                        naphthol-7-                                                                           2-aminophenol                                                                          naphthol-6-                                                                           propionyl-                                           sulphonic        sulphonic acid                                                                        chloride                                             acid                                                             35 1-amino-2-naphthol-                                                                     2-amino-5-                                                                            4,6-dinitro-2-                                                                         2-amino-8-                                                                            chloroacetyl                                                                           black                             4-sulphonic acid                                                                        naphthol-7-                                                                           aminophenol                                                                            naphthol-6-                                                                           chloride                                             sulphonic        sulphonic acid                                               acid                                                             36 1-amino-2-naphthol-                                                                     2-amino-5-                                                                            4-nitro-6-acetyl-                                                                      2-amino-8-                                                                            α, β-dibromo-                                                               black                             4-sulphonic acid                                                                        naphthol-7-                                                                           amino-2-amino-                                                                         naphthol-6-                                                                           propionyl-                                           sulphonic                                                                             phenol   sulphonic acid                                                                        chloride                                             acid                                                             37 1-amino-2-naphthol-                                                                     2-amino-5-                                                                            4-chloro-2-amino-                                                                      1-amino-5-                                                                            α, β-dibromo-                                                               navy                              4-sulphonic acid                                                                        naphthol-7-                                                                           phenol   naphthol-7-                                                                           propionyl-                                                                             blue                                        sulphonic        sulphonic acid                                                                        chloride                                             acid                                                             38 1-amino-2-naphthol-                                                                     2-amino-5-                                                                            5-nitro-4-chloro-                                                                      1-amino-5-                                                                            α, β-dibromo-                                                               navy                              4-sulphonic acid                                                                        naphthol-7-                                                                           2-aminophenol                                                                          naphthol-7-                                                                           propionyl-                                                                             blue                                        sulphonic        sulphonic acid                                                                        chloride                                             acid                                                             __________________________________________________________________________

EXAMPLE 9

53.4 Parts of the 1:1 chromium complex of the monoazo dye fromdiazotised 6-nitro-1-amino-2-naphthol-4-sulphonic acid and2-amino-5-naphthol-7-sulphonic acid and 40.4 parts of the monoazo dyefrom diazotised 4-nitro-2-aminobenzene and2-amino-8-naphthol-6-sulphonic acid are suspended in 600 parts of water.This suspension is adjusted to a pH value of 8 to 9 by addition of a 2Nsolution of sodium hydroxide and reacted to give the homogeneous mixedcomplex by stirring for 1 hour at 90° to 95° C. The deep black reactionsolution is cooled to 0° C. by the addition of ice and thereaftertreated slowly with vigorous stirring, with 20 parts oftrifluorotriazine while keeping a pH value of 6.5 to 7 by the dropwiseaddition of a dilute sodium hydroxide solution. As soon as the pH valueno longer changes, the reaction mixture is treated with 24 parts of2-toluididine and stirred to 40° C. with attendant rise in temperatureuntil the pH value kept between 7 and 7.5 by the dropwise addition ofdilute sodium hydroxide solution no longer changes.

The bisacylated mixed complex of the following constitution ##STR12## isprecipitated from the solution by the addition of sodium chloride,isolated by filtration, washed with a dilute sodium chloride solution,and dried in vacuo at 60° to 70° C. The readily soluble dye gives fullblack shades of very good fastness properties on cotton fabric andshrinkproofed woollen fabric.

A black mixed complex of similar colouristic properties is obtained bybisacylating the mixed complex obtained from the reaction at atemperature of 20° to 25° C. with 36.5 parts of5-chloro-2,4,6-trifluoropyrimidine while maintaining a pH of 6.5 to 7and then isolating it by evaporation.

DYEING PROCEDURE 1

The following ingredients are dissolved in succession in 4000 parts ofwater of 50° C.: 4 parts of 80% acetic acid, 2 parts of the ammoniumsalt of the acid sulphuric acid ester of the adduct of a fatty amine(consisting of 30% of hexadecylamine, 25% of octadecylamine and 45% ofoctadecylamine and 7 moles of ethylene oxide) and 4 parts of ammoniumsulphate. Then 8 parts of the dye obtained in Example 1 are dissolvedhot in 100 parts of water and added to this dyebath. Then 100 parts ofprewetted wool knitting yarn are put into the bath and the bathtemperature is raised from 50° to 80° C. in the course of 30 minutes.After dyeing for 20 minutes at 80° C., the bath is heated to the boiland dyeing is subsequently carried out at the boil for 90 minutes. Thedye exhausts almost completely onto the substrate. After the bath hasbeen cooled to 80° C., the pH is raised from app. 4.5 to a constant 8.5by adding ammonia solution and the goods are given an after-treatmentfor 20 minutes at this temperature. After a thorough rinsing with hotand cold water, acidifying with 1 part of 80% formic acid, centrifugingand drying, a deep black woollen yarn of very good wetfastness andfastness to rubbing and of excellent light-fastness is obtained.

DYEING PROCEDURE 2

A shrinkproofed woollen fabric is impregnated with the followingpreparation and squeezed out on a padder to a liquor pick-up of 250%.

    ______________________________________                                        4      parts of Diaprint REG (acid-resistant thickener)                       1      part of sulphamic acid                                                 0.2    part of thymol                                                         0.2    part of emulsifier                                                     94.6   part of water                                                          100    parts.                                                                 ______________________________________                                    

The impregnated material is subsequently brought into contact with atransfer paper carrying a printing design applied in the conventionalmanner with the dye of Example 3 and the transfer is effected in aheatable press for 3 minutes at 100° C. to 105° C., applying a pressureof approx. 0.5 kg/cm². After the woollen fabric has been rinsed anddried, it has a corresponding deep black printed design of very goodfastness properties.

DYEING PROCEDURE 3

A chlorinated wool flannel fabric is impregnated with the following dyepreparation and squeezed out to a 100% pickup:

    ______________________________________                                        50     parts of the dye of Example 1                                          300    parts of urea                                                          320    parts of Solvitose OFA, 4% (thickener)                                 10     parts of a mixture of anionic fatty alcohol ether                             sulphate with non-ionogenic wetting agents                             10     parts of the leveller used in Example 1                                10     parts of sodium metabisulphate                                         10     parts of 80% acetic acid                                               280    parts of water                                                         1000   parts of padding liquor.                                               ______________________________________                                    

The impregnated fabric is rolled up and packed airtight and subsequentlystored for 48 hours at room temperature. After rinsing with cold water,the material is treated in a fresh bath with sufficient 24% ammonia toattain a pH value of 8.5 and kept for 15 minutes at 80° C. After rinsingto warm water, the fabric is acidified with 80% acetic acid and dried.The woollen fabric is dyed in a full black shade of excellent fastnessproperties.

DYEING PROCEDURE 4

2 Parts of the dye obtained in Example 9 are dissolved in 100 parts ofwater with the simultaneous addition of 0.5 part of sodiumm-nitrobenzene-sulphonate. A cotton fabric is impregnated with theresultant solution to a liquor pick-up of 75% and then dried. The fabricis thereafter impregnated with a warm solution of 20° C. which contains,per liter, 5 g of sodium hydroxide and 300 g of sodium chloride,squeezed out to a pick-up of 75%, steamed for 30 seconds at 100° to 101°C., rinsed, soaped for a quarter of an hour in a 0.3% boiling solutionof a non-ionic detergent, rinsed again, and dried.

DYEING PROCEDURE 5

2 Parts of the dye of Example 9 are dissolved in 100 parts of water.This solution is added to 1900 parts of cold water, 60 parts of sodiumchloride are added and 100 parts of a cotton fabric are put into thisdyebath. The temperature is raised to 40° C. and after 30 minutes 40parts of calcined sodium carbonate and a further 60 parts of sodiumchloride are added. The temperature is kept for 30 minutes at 40° C. andthe dyeing is rinsed, then soaped for 15 minutes in a 0.3% boilingsolution of a non-ionic detergent, rinsed again and dried.

What we claim is:
 1. A process for dyeing or printing a substrate ofcellulose or shrinkproofed wool, comprising the step of applying to thesubstrate a chromium complex dye of the formula ##STR13## wherein thering a is substituted by 4- or 5-nitro, and M is a cation.
 2. Theprocess of claim 1, wherein in the chromium complex dye the nitrosubstituent is in the 4-position.
 3. Cellulose or shrinkproofed wooldyed or printed with a chromium complex dye of the formula ##STR14##wherein the ring a is substituted 4- or 5-nitro, and M is a cation. 4.Cellulose or shrinkproofed wool dyed or printed with the chromiumcomplex dye of claim 3, wherein the nitro substituent is in the4-position.